CN106587971A - Multiferroic composite ceramics with softened magnetic hysteresis loops and preparation method for multiferroic composite ceramics - Google Patents

Multiferroic composite ceramics with softened magnetic hysteresis loops and preparation method for multiferroic composite ceramics Download PDF

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CN106587971A
CN106587971A CN201611162388.0A CN201611162388A CN106587971A CN 106587971 A CN106587971 A CN 106587971A CN 201611162388 A CN201611162388 A CN 201611162388A CN 106587971 A CN106587971 A CN 106587971A
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hysteresis curve
composite ceramicses
multiferroic composite
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蒲永平
高子岩
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Shaanxi University of Science and Technology
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Abstract

The invention discloses multiferroic composite ceramics with softened magnetic hysteresis loops and a preparation method for the multiferroic composite ceramics and belongs to the technical field of material preparation. The chemical composition of the composite ceramics is expressed by BaTiO3-BaFe<12-x>(Co0.5Ti0.5)xO19, wherein x is greater than 0 and is not greater than 2. According to the multiferroic composite ceramics and the preparation method therefor, BaTiO3-BaFe12O19 serves as a matrix, the resistivity of the matrix is improved greatly through doping Co<2+> and Ti<4+>, and then, the dielectric properties are improved. A practical and feasible method is provided for the practical application of the multiferroic composite ceramics. A microwave sintering method is different from general traditional sintering methods, the sintering time is very short, and a sintering process is free of temperature gradients; and nano-powder sintered ceramics prepared by the method and a microwave hydrothermal method have the advantages of small grain size, high density, and the like.

Description

One kind softens hysteresis curve multiferroic composite ceramicses and preparation method thereof
Technical field
The invention belongs to technical field of material, is related to the preparation method of multi-ferroic material, and in particular to one kind softens Hysteresis curve multiferroic composite ceramicses and preparation method thereof.
Background technology
Also known as magnetoelectric material, it refers to and have simultaneously two or more basic ferrum (ferroelectricity, ferrum multi-ferroic material Magnetic and ferroelasticity) material, the research of multi-ferroic material is inseparable, same material with the research of magnetoelectric effect Middle magnetic and ferroelectricity coexist so that multi-ferroic material not only can make as single magnetic material and ferroelectric substance With, meanwhile, magnetic causes material magnetization or additional magnetic field to cause thing with electric coupling effect, i.e. extra electric field in multi-ferroic material Occurs electric polarization inside matter so that the material has in the application higher degree of freedom, is the miniaturization and multifunction of device There is provided possible.
Typically there is designability, controllable by ferroelectric phase with the ferromagnetic mutually biphase magnetoelectricity multiferroic composite ceramicses for constituting Property, at room temperature there is higher magnetoelectric effect than single-phase multi-ferroic material.However, the performance of multiferroic composite ceramicses takes Certainly suitably constitute phase, biphase connectedness, volume fraction, crystallite dimension and shape etc. factor in material.Because BaTiO3 It is typical ferroelectric phase, BaFe12O19It is typical ferromagnetic phase, so BaTiO3-BaFe12O19It is that most important multiferroic is combined One of the research system of ceramics (Zijing Dong, et al.Fabrication, structure and properties of BaTiO3–BaFe12O19composites with core–shell heterostructure[J].Journal of the European Ceramic Society,2015,35:3513-3520).Typically there is high resistivity to be magnetic electric compound material Obtain the precondition of excellent magnetic electricity performance.BaTiO3-BaFe12O19BaFe in composite ceramicses system12O19Resistivity ratio BaTiO3Low several orders of magnitude, the movement that will necessarily there is electric charge after being combined in two-phase interface.Increase is led in the leakage for causing material, damages Consumption increase, dielectric properties deteriorate.
The content of the invention
It is an object of the invention to provide a kind of soften hysteresis curve multiferroic composite ceramicses and preparation method thereof, to overcome The defect that above-mentioned prior art is present, simple to operate, reproducible, composite ceramicses dielectric constant obtained in Jing the method for the invention Height, loss is little, and resistivity is higher.
To reach above-mentioned purpose, the present invention is adopted the following technical scheme that：
One kind softens hysteresis curve multiferroic composite ceramicses, and the chemical formula of the composite ceramicses is：BaTiO3-BaFe12-x (Co0.5Ti0.5)xO19, wherein：0 ＜ x≤2.
A kind of preparation method for softening hysteresis curve multiferroic composite ceramicses, the chemical formula of the composite ceramicses is： BaTiO3-BaFe12-x(Co0.5Ti0.5)xO19, wherein：0 ＜ x≤2, comprise the following steps：
1) according to TiCl4：BaCl2·2H2O：KOH=1：2：10 mol ratio weighs TiCl4、BaCl2·2H2O and KOH；
2) by TiCl4And BaCl2·2H2O is dissolved in distilled water and obtains mixed solution, then KOH is added into mixed solution In obtain precursor liquid；
3) by precursor liquid at 180～220 DEG C, microwave hydrothermal reacts 25～35min, and product A is obtained, and reaction is produced Thing A is washed to neutrality；
4) by BaFe12-x(Co0.5Ti0.5)xO19Middle Ba2+, Fe3+, Co2+, Ti4+Mol ratio, weigh Ba (NO3)2, TiCl4, Co(NO3)2·6H2O and Fe (NO3)3·9H2O, in being dissolved in distilled water, adjusts pH value of solution >=13, alkaline solution is obtained, by this At 170～190 DEG C, 25～30min of microwave hydrothermal is obtained product B to alkaline solution, and product B is washed to into neutrality；
5) by step 3) obtained in product A and step 4) obtained in product B mixing post-drying, obtain mixed powder Body, adds binding agent, then carries out pelletize, compressing, prepared base substrate；
6) by base substrate dumping, ceramic green is obtained, then sinters ceramic green under microwave condition, be obtained and soften magnetic hysteresis Loop line multiferroic composite ceramicses.
Further, step 2) in the mixed solution that obtains the solubility of titanium ion be 0.3mol/L.
Further, step 5) in binding agent be PVA solution, and the volume solubility of PVA solution be 5%.
Further, step 5) in binding agent addition for mixed powder quality 5%～10%.
Further, step 6) in dumping be specially：With the heating rate of 2 DEG C/min from room temperature to 200 DEG C, then 500 DEG C are warmed up to from 200 DEG C with the heating rate of 3 DEG C/min, finally 600 is warmed up to from 500 DEG C with the programming rate of 5 DEG C/min DEG C and be incubated 2h, then furnace cooling.
Further, step 6) in microwave power be 1500W.
Further, step 6) in sintering be specially：With the heating rate of 25 DEG C/min from room temperature to 1000 DEG C～ 1100 DEG C and 5min is incubated, then furnace cooling.
Further, TiCl4、BaCl2·2H2O、Co(NO3)2·6H2O、Fe(NO3)3·9H2O, KOH and Ba (NO3)2's Purity is more than 99.0%.
Compared with prior art, the present invention has following beneficial technique effect：
The present invention is by the Co that adulterates2+And Ti4+Ion, improves resistivity, softens hysteresis curve, improves BaFe12O19Property Can, so as to keep material ferromagnetic property on the premise of, improve BaTiO3-BaFe12O19The ferroelectric properties of composite ceramicses so as to many ferrum Performance further meets practical application, prepares powder body using microwave-hydrothermal method in addition, little with crystal grain, size uniform, degree of crystallinity Height, the advantages of the response time is short, using microwave sintering method sintering ceramics, different from general conventional sintering, sintering time is short, burns There is no thermograde during knot, the method combines the ceramics of nano-powder sintering prepared by microwave-hydrothermal method and has crystal grain chi It is very little little, many advantages, such as consistency is high, with TiCl4、BaCl2·2H2O、Co(NO3)2·6H2O、Fe(NO3)3·9H2O, KOH and Ba(NO3)2For raw material, raw material is simple, cheap.
Further, the present invention improves many by controlling reaction condition, the high resistivity multiferroic composite ceramicses of preparation Ferrum BaTiO3-BaFe12O19Ferroelectric properties, size uniform little with crystal grain, degree of crystallinity is high, and dielectric constant is high, be lost it is little, The advantages of hysteresis curve coercive field is little, is multiferroic BaTiO3-BaFe12O19The practical application of composite ceramicses provides a kind of practical Feasible method.
Description of the drawings
Fig. 1 is the XRD spectrum of softening hysteresis curve multiferroic composite ceramic material prepared by the present invention；
Fig. 2 is the SEM photograph of softening hysteresis curve multiferroic composite ceramicses prepared by the present invention；Wherein, (a), (b), C (), (d), (e) are respectively the composite ceramicses of x=0,0.5,1,1.5,2；
Fig. 3 is the change collection of illustrative plates of the resistivity of softening hysteresis curve multiferroic composite ceramicses prepared by the present invention；
Fig. 4 (a) is the change collection of illustrative plates of the dielectric constant of softening hysteresis curve multiferroic composite ceramicses prepared by the present invention；
Fig. 4 (b) is the change collection of illustrative plates of the loss with frequency of softening hysteresis curve multiferroic composite ceramicses prepared by the present invention；
Fig. 5 is the ferroelectric hysteresis loop of softening hysteresis curve multiferroic composite ceramic material prepared by the present invention；
Fig. 6 is the hysteresis curve of softening hysteresis curve multiferroic composite ceramic material prepared by the present invention.
Specific embodiment
The present invention is described in further detail below：
One kind softens hysteresis curve multiferroic composite ceramicses, and the chemical formula of the composite ceramicses is：BaTiO3-BaFe12-x (Co0.5Ti0.5)xO19, wherein：0 ＜ x≤2.
A kind of preparation method for softening hysteresis curve multiferroic composite ceramicses, the chemical formula of the composite ceramicses is： BaTiO3-BaFe12-x(Co0.5Ti0.5)xO19, wherein：0 ＜ x≤2, comprise the following steps：
1) according to TiCl4：BaCl2·2H2O：KOH=1：2：10 mol ratio weighs TiCl4、BaCl2·2H2O and KOH；
2) by TiCl4And BaCl2·2H2O is dissolved in distilled water and obtains mixed solution, and titanium ion is molten in mixed solution Spend for 0.3mol/L, then KOH is added in mixed solution and obtained precursor liquid；
3) by precursor liquid at 180～220 DEG C, microwave hydrothermal reacts 25～35min, and product A is obtained, and reaction is produced Thing A is washed to neutrality；
4) by BaFe12-x(Co0.5Ti0.5)xO19Middle Ba2+, Fe3+, Co2+, Ti4+Mol ratio, weigh Ba (NO3)2, TiCl4, Co(NO3)2·6H2O and Fe (NO3)3·9H2O, in being dissolved in distilled water, adjusts pH value of solution >=13, alkaline solution is obtained, by this At 170～190 DEG C, 25～30min of microwave hydrothermal is obtained product B to alkaline solution, and product B is washed to into neutrality；
5) by step 3) obtained in product A and step 4) obtained in product B mixing post-drying, obtain mixed powder Body, adds binding agent, and the addition of binding agent is the 5%～10% of mixed powder quality, and the binding agent is PVA solution, And the volume solubility of PVA solution is 5%, pelletize, compressing, prepared base substrate are then carried out；
6) by base substrate dumping, with the heating rate of 2 DEG C/min from room temperature to 200 DEG C, then with the intensification of 3 DEG C/min Speed is warmed up to 500 DEG C from 200 DEG C, finally 600 DEG C is warmed up to from 500 DEG C with the programming rate of 5 DEG C/min and is incubated 2h, then Furnace cooling, obtains ceramic green, then by ceramic green under the microwave power of 1500W with the heating rate of 25 DEG C/min from Room temperature to 1000 DEG C～1100 DEG C is simultaneously incubated 5min, then furnace cooling, is obtained and softens hysteresis curve multiferroic composite ceramic Porcelain.
Wherein, raw materials used TiCl4、BaCl2·2H2O、Co(NO3)2·6H2O、Fe(NO3)3·9H2O, KOH and Ba (NO3)2Purity be more than 99.0%.
The present invention is described in further detail with reference to embodiment：
Blank example
One kind softens hysteresis curve multiferroic composite ceramicses, and the chemical formula of the composite ceramicses is：BaTiO3-BaFe12-x (Co0.5Ti0.5)xO19, wherein：X=0.
A kind of preparation method for softening hysteresis curve multiferroic composite ceramicses, the chemical formula of the composite ceramicses is： BaTiO3-BaFe12O19, comprise the following steps：
1) according to TiCl4：BaCl2·2H2O：KOH=1：2：10 mol ratio weighs TiCl4、BaCl2·2H2O and KOH；
2) by TiCl4And BaCl2·2H2O is dissolved in distilled water and obtains mixed solution, and titanium ion is molten in mixed solution Spend for 0.3mol/L, then KOH is added in mixed solution and obtained precursor liquid；
3) by precursor liquid at 200 DEG C, microwave hydrothermal reaction 30min is obtained product A, and product A is washed to It is neutral；
4) by BaFe12O19Middle Ba2+, Fe3+Mol ratio, weigh Ba (NO3)2With Fe (NO3)3·9H2O, is dissolved in distillation In water, pH value of solution >=13 are adjusted, alkaline solution is obtained, by the alkaline solution at 180 DEG C, microwave hydrothermal 28min is obtained reaction Product B, by product B neutrality is washed to；
5) by step 3) obtained in product A and step 4) obtained in product B mixing post-drying, obtain mixed powder Body, adds binding agent, and the addition of binding agent is the 5% of mixed powder quality, and the binding agent is PVA solution, and PVA is molten The volume solubility of liquid is 5%, then carries out pelletize, compressing, prepared base substrate；
6) by base substrate dumping, with the heating rate of 2 DEG C/min from room temperature to 200 DEG C, then with the intensification of 3 DEG C/min Speed is warmed up to 500 DEG C from 200 DEG C, finally 600 DEG C is warmed up to from 500 DEG C with the programming rate of 5 DEG C/min and is incubated 2h, then Furnace cooling, obtains ceramic green, then by ceramic green under the microwave power of 1500W with the heating rate of 25 DEG C/min from Room temperature is to 1050 DEG C and is incubated 5min, then furnace cooling, is obtained and softens hysteresis curve multiferroic composite ceramicses.
Embodiment 1
One kind softens hysteresis curve multiferroic composite ceramicses, and the chemical formula of the composite ceramicses is：BaTiO3-BaFe12-x (Co0.5Ti0.5)xO19, wherein：X=0.5.
A kind of preparation method for softening hysteresis curve multiferroic composite ceramicses, the chemical formula of the composite ceramicses is： BaTiO3-BaFe12-x(Co0.5Ti0.5)xO19, wherein：X=0.5, comprises the following steps：
1) according to TiCl4：BaCl2·2H2O：KOH=1：2：10 mol ratio weighs TiCl4、BaCl2·2H2O and KOH；
2) by TiCl4And BaCl2·2H2O is dissolved in distilled water and obtains mixed solution, and titanium ion is molten in mixed solution Spend for 0.3mol/L, then KOH is added in mixed solution and obtained precursor liquid；
3) by precursor liquid at 180 DEG C, microwave hydrothermal reaction 35min is obtained product A, and product A is washed to It is neutral；
4) by BaFe12-x(Co0.5Ti0.5)xO19Middle Ba2+, Fe3+, Co2+, Ti4+Mol ratio, weigh Ba (NO3)2, TiCl4, Co(NO3)2·6H2O and Fe (NO3)3·9H2O, in being dissolved in distilled water, adjusts pH value of solution >=13, alkaline solution is obtained, by this At 170 DEG C, microwave hydrothermal 30min is obtained product B to alkaline solution, and product B is washed to into neutrality；
5) by step 3) obtained in product A and step 4) obtained in product B mixing post-drying, obtain mixed powder Body, adds binding agent, and the addition of binding agent is the 10% of mixed powder quality, and the binding agent is PVA solution, and PVA The volume solubility of solution is 5%, then carries out pelletize, compressing, prepared base substrate；
6) by base substrate dumping, with the heating rate of 2 DEG C/min from room temperature to 200 DEG C, then with the intensification of 3 DEG C/min Speed is warmed up to 500 DEG C from 200 DEG C, finally 600 DEG C is warmed up to from 500 DEG C with the programming rate of 5 DEG C/min and is incubated 2h, then Furnace cooling, obtains ceramic green, then by ceramic green under the microwave power of 1500W with the heating rate of 25 DEG C/min from Room temperature is to 1000 DEG C and is incubated 5min, then furnace cooling, is obtained and softens hysteresis curve multiferroic composite ceramicses.
Embodiment 2
One kind softens hysteresis curve multiferroic composite ceramicses, and the chemical formula of the composite ceramicses is：BaTiO3-BaFe12-x (Co0.5Ti0.5)xO19, wherein：X=1.0.
A kind of preparation method for softening hysteresis curve multiferroic composite ceramicses, the chemical formula of the composite ceramicses is： BaTiO3-BaFe12-x(Co0.5Ti0.5)xO19, wherein：X=1.0, comprises the following steps：
1) according to TiCl4：BaCl2·2H2O：KOH=1：2：10 mol ratio weighs TiCl4、BaCl2·2H2O and KOH；
2) by TiCl4And BaCl2·2H2O is dissolved in distilled water and obtains mixed solution, and titanium ion is molten in mixed solution Spend for 0.3mol/L, then KOH is added in mixed solution and obtained precursor liquid；
3) by precursor liquid at 220 DEG C, microwave hydrothermal reaction 25min is obtained product A, and product A is washed to It is neutral；
4) by BaFe12-x(Co0.5Ti0.5)xO19Middle Ba2+, Fe3+, Co2+, Ti4+Mol ratio, weigh Ba (NO3)2, TiCl4, Co(NO3)2·6H2O and Fe (NO3)3·9H2O, in being dissolved in distilled water, adjusts pH value of solution >=13, alkaline solution is obtained, by this At 190 DEG C, microwave hydrothermal 25min is obtained product B to alkaline solution, and product B is washed to into neutrality；
5) by step 3) obtained in product A and step 4) obtained in product B mixing post-drying, obtain mixed powder Body, adds binding agent, and the addition of binding agent is the 8% of mixed powder quality, and the binding agent is PVA solution, and PVA is molten The volume solubility of liquid is 5%, then carries out pelletize, compressing, prepared base substrate；
6) by base substrate dumping, with the heating rate of 2 DEG C/min from room temperature to 200 DEG C, then with the intensification of 3 DEG C/min Speed is warmed up to 500 DEG C from 200 DEG C, finally 600 DEG C is warmed up to from 500 DEG C with the programming rate of 5 DEG C/min and is incubated 2h, then Furnace cooling, obtains ceramic green, then by ceramic green under the microwave power of 1500W with the heating rate of 25 DEG C/min from Room temperature is to 1100 DEG C and is incubated 5min, then furnace cooling, is obtained and softens hysteresis curve multiferroic composite ceramicses.
Embodiment 3
One kind softens hysteresis curve multiferroic composite ceramicses, and the chemical formula of the composite ceramicses is：BaTiO3-BaFe12-x (Co0.5Ti0.5)xO19, wherein：X=1.5.
A kind of preparation method for softening hysteresis curve multiferroic composite ceramicses, the chemical formula of the composite ceramicses is： BaTiO3-BaFe12-x(Co0.5Ti0.5)xO19, wherein：X=1.5, comprises the following steps：
1) according to TiCl4：BaCl2·2H2O：KOH=1：2：10 mol ratio weighs TiCl4、BaCl2·2H2O and KOH；
2) by TiCl4And BaCl2·2H2O is dissolved in distilled water and obtains mixed solution, and titanium ion is molten in mixed solution Spend for 0.3mol/L, then KOH is added in mixed solution and obtained precursor liquid；
3) by precursor liquid at 200 DEG C, microwave hydrothermal reaction 30min is obtained product A, and product A is washed to It is neutral；
4) by BaFe12-x(Co0.5Ti0.5)xO19Middle Ba2+, Fe3+, Co2+, Ti4+Mol ratio, weigh Ba (NO3)2, TiCl4, Co(NO3)2·6H2O and Fe (NO3)3·9H2O, in being dissolved in distilled water, adjusts pH value of solution >=13, alkaline solution is obtained, by this At 180 DEG C, microwave hydrothermal 28min is obtained product B to alkaline solution, and product B is washed to into neutrality；
5) by step 3) obtained in product A and step 4) obtained in product B mixing post-drying, obtain mixed powder Body, adds binding agent, and the addition of binding agent is the 5% of mixed powder quality, and the binding agent is PVA solution, and PVA is molten The volume solubility of liquid is 5%, then carries out pelletize, compressing, prepared base substrate；
6) by base substrate dumping, with the heating rate of 2 DEG C/min from room temperature to 200 DEG C, then with the intensification of 3 DEG C/min Speed is warmed up to 500 DEG C from 200 DEG C, finally 600 DEG C is warmed up to from 500 DEG C with the programming rate of 5 DEG C/min and is incubated 2h, then Furnace cooling, obtains ceramic green, then by ceramic green under the microwave power of 1500W with the heating rate of 25 DEG C/min from Room temperature is to 1050 DEG C and is incubated 5min, then furnace cooling, is obtained and softens hysteresis curve multiferroic composite ceramicses.
Embodiment 4
One kind softens hysteresis curve multiferroic composite ceramicses, and the chemical formula of the composite ceramicses is：BaTiO3-BaFe12-x (Co0.5Ti0.5)xO19, wherein：X=2.0.
A kind of preparation method for softening hysteresis curve multiferroic composite ceramicses, the chemical formula of the composite ceramicses is： BaTiO3-BaFe12-x(Co0.5Ti0.5)xO19, wherein：X=2.0, comprises the following steps：
1) according to TiCl4：BaCl2·2H2O：KOH=1：2：10 mol ratio weighs TiCl4、BaCl2·2H2O and KOH；
2) by TiCl4And BaCl2·2H2O is dissolved in distilled water and obtains mixed solution, and titanium ion is molten in mixed solution Spend for 0.3mol/L, then KOH is added in mixed solution and obtained precursor liquid；
3) by precursor liquid at 180 DEG C, microwave hydrothermal reaction 25min is obtained product A, and product A is washed to It is neutral；
4) by BaFe12-x(Co0.5Ti0.5)xO19Middle Ba2+, Fe3+, Co2+, Ti4+Mol ratio, weigh Ba (NO3)2, TiCl4, Co(NO3)2·6H2O and Fe (NO3)3·9H2O, in being dissolved in distilled water, adjusts pH value of solution >=13, alkaline solution is obtained, by this At 190 DEG C, microwave hydrothermal 30min is obtained product B to alkaline solution, and product B is washed to into neutrality；
5) by step 3) obtained in product A and step 4) obtained in product B mixing post-drying, obtain mixed powder Body, adds binding agent, and the addition of binding agent is the 5% of mixed powder quality, and the binding agent is PVA solution, and PVA is molten The volume solubility of liquid is 5%, then carries out pelletize, compressing, prepared base substrate；
6) by base substrate dumping, with the heating rate of 2 DEG C/min from room temperature to 200 DEG C, then with the intensification of 3 DEG C/min Speed is warmed up to 500 DEG C from 200 DEG C, finally 600 DEG C is warmed up to from 500 DEG C with the programming rate of 5 DEG C/min and is incubated 2h, then Furnace cooling, obtains ceramic green, then by ceramic green under the microwave power of 1500W with the heating rate of 25 DEG C/min from Room temperature is to 1100 DEG C and is incubated 5min, then furnace cooling, is obtained and softens hysteresis curve multiferroic composite ceramicses.
Referring to Fig. 1 and Fig. 2, the BaTiO prepared by above example3-BaFe12-x(Co0.5Ti0.5)xO19Composite ceramic material As can be seen that having synthesized BaTiO in above example in XRD spectrum and SEM photograph3And BaFe12-x(Co0.5Ti0.5)xO19 The composite ceramicses for mutually coexisting.Simultaneously, it can be seen that without other dephasigns presence, and this biphase degree of crystallinity is higher, without mutually contrary Should, chemical compatibility is preferable.Referring to Fig. 3, it can be seen that resistivity gradually increases with the increase of component.Referring to Fig. 4, can be with Find out that dielectric constant reaches more than 10000, dielectric properties are excellent.Referring to Fig. 5, composite ceramicses have more saturated ferroelectric hysteresis loop, The ferroelectricity of optimum is obtained in x=1.Referring to Fig. 6, it can be seen that by the Co that adulterates2+And Ti4+The saturation magnetic of composite ceramicses Change intensity and still remain in higher level, coercive field is gradually reduced.
In sum, the present invention is prepared for BaTiO by microwave-hydrothermal method and microwave sintering method3-BaFe12-x (Co0.5Ti0.5)xO19Composite ceramicses.With BaTiO3-BaFe12-x(Co0.5Ti0.5)xO19Based on, by the Co that adulterates2+, Ti4+Greatly Improve its resistivity, and then improve dielectric properties.And microwave sintering method is different from general conventional sintering, sintering time It is very short, there is no thermograde in sintering process, the method combines the ceramics tool of nano-powder sintering prepared by microwave-hydrothermal method Have many advantages, such as crystallite dimension is little, and consistency is high, for Multiferroic composite material practical application provide it is a kind of practical Method.Employing BaTiO disclosed by the invention3-BaFe12-x(Co0.5Ti0.5)xO19Composite ceramicses and preparation method thereof are possible to into To prepare Multiferroic composite material technically and financially simultaneous excellent new formula.

Claims (9)

1. it is a kind of to soften hysteresis curve multiferroic composite ceramicses, it is characterised in that the chemical formula of the composite ceramicses is：BaTiO3- BaFe12-x(Co0.5Ti0.5)xO19, wherein：0 ＜ x≤2.
2. it is a kind of soften hysteresis curve multiferroic composite ceramicses preparation method, it is characterised in that the chemistry of the composite ceramicses Formula is：BaTiO3-BaFe12-x(Co0.5Ti0.5)xO19, wherein：0 ＜ x≤2, comprise the following steps：
1) according to TiCl4：BaCl2·2H2O：KOH=1：2：10 mol ratio weighs TiCl4、BaCl2·2H2O and KOH；
2) by TiCl4And BaCl2·2H2O is dissolved in distilled water and obtains mixed solution, then adds in mixed solution KOH and obtains To precursor liquid；
3) by precursor liquid at 180～220 DEG C, microwave hydrothermal reacts 25～35min, product A is obtained, by product A It is washed to neutrality；
4) by BaFe12-x(Co0.5Ti0.5)xO19Middle Ba2+, Fe3+, Co2+, Ti4+Mol ratio, weigh Ba (NO3)2, TiCl4, Co (NO3)2·6H2O and Fe (NO3)3·9H2O, in being dissolved in distilled water, adjusts pH value of solution >=13, alkaline solution is obtained, by the alkali Property solution at 170～190 DEG C, 25～30min of microwave hydrothermal, be obtained product B, product B is washed to into neutrality；
5) by step 3) obtained in product A and step 4) obtained in product B mixing post-drying, obtain mixed powder, Binding agent is added, pelletize, compressing, prepared base substrate is then carried out；
6) by base substrate dumping, ceramic green is obtained, then sinters ceramic green under microwave condition, be obtained and soften hysteresis curve Multiferroic composite ceramicses.
3. it is according to claim 1 it is a kind of soften hysteresis curve multiferroic composite ceramicses preparation method, it is characterised in that Step 2) in the mixed solution that obtains the solubility of titanium ion be 0.3mol/L.
4. it is according to claim 1 it is a kind of soften hysteresis curve multiferroic composite ceramicses preparation method, it is characterised in that Step 5) in binding agent be PVA solution, and the volume solubility of PVA solution be 5%.
5. it is according to claim 1 it is a kind of soften hysteresis curve multiferroic composite ceramicses preparation method, it is characterised in that Step 5) in binding agent addition for mixed powder quality 5%～10%.
6. it is according to claim 1 it is a kind of soften hysteresis curve multiferroic composite ceramicses preparation method, it is characterised in that Step 6) in dumping be specially：With the heating rate of 2 DEG C/min from room temperature to 200 DEG C, then with the intensification speed of 3 DEG C/min Rate is warmed up to 500 DEG C from 200 DEG C, finally 600 DEG C is warmed up to from 500 DEG C with the programming rate of 5 DEG C/min and is incubated 2h, Ran Housui Stove is cooled down.
7. it is according to claim 1 it is a kind of soften hysteresis curve multiferroic composite ceramicses preparation method, it is characterised in that Step 6) in microwave power be 1500W.
8. it is according to claim 1 it is a kind of soften hysteresis curve multiferroic composite ceramicses preparation method, it is characterised in that Step 6) in sintering be specially：So that the heating rate of 25 DEG C/min is from room temperature to 1000 DEG C～1100 DEG C and is incubated 5min, Then furnace cooling.
9. it is according to claim 1 it is a kind of soften hysteresis curve multiferroic composite ceramicses preparation method, it is characterised in that TiCl4、BaCl2·2H2O、Co(NO3)2·6H2O、Fe(NO3)3·9H2O, KOH and Ba (NO3)2Purity be 99.0% with On.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107935593A (en) * 2017-12-20 2018-04-20 西安交通大学 One kind has ultralow hysteresis electric field induced strain ferroelectric ceramic material and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101708991A (en) * 2009-11-11 2010-05-19 沈阳师范大学 Method for preparing barium ferrite with low coercive force temperature coefficient
CN101921111A (en) * 2010-07-12 2010-12-22 陕西科技大学 Method for preparing MnNb2O6 microwave medium ceramic powder by utilizing hydrothermal method
CN102491428A (en) * 2011-11-16 2012-06-13 陕西科技大学 Method for preparing hexagonal BeFe12O19 (barium ferrite) magnetic nano powder by microwave-hydrothemal method
CN103274677A (en) * 2013-05-27 2013-09-04 浙江大学 Titanium-doped barium ferrite ceramic material and preparation method thereof
CN105645944A (en) * 2015-12-30 2016-06-08 陕西科技大学 Bi2Fe4O9/BaFe12O19 (bismuth ferrite/barium ferrite) composite ceramic and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101708991A (en) * 2009-11-11 2010-05-19 沈阳师范大学 Method for preparing barium ferrite with low coercive force temperature coefficient
CN101921111A (en) * 2010-07-12 2010-12-22 陕西科技大学 Method for preparing MnNb2O6 microwave medium ceramic powder by utilizing hydrothermal method
CN102491428A (en) * 2011-11-16 2012-06-13 陕西科技大学 Method for preparing hexagonal BeFe12O19 (barium ferrite) magnetic nano powder by microwave-hydrothemal method
CN103274677A (en) * 2013-05-27 2013-09-04 浙江大学 Titanium-doped barium ferrite ceramic material and preparation method thereof
CN105645944A (en) * 2015-12-30 2016-06-08 陕西科技大学 Bi2Fe4O9/BaFe12O19 (bismuth ferrite/barium ferrite) composite ceramic and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
WANT, BD等: "Dielectric, ferroelectric and magnetic behavior of BaTiO3-BaFe12O19 composite", 《JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS》 *
聂海等: "M型钡铁氧体掺杂CO-Ti改性研究", 《材料研究学报》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107935593A (en) * 2017-12-20 2018-04-20 西安交通大学 One kind has ultralow hysteresis electric field induced strain ferroelectric ceramic material and preparation method thereof
CN107935593B (en) * 2017-12-20 2021-08-13 西安交通大学 Ferroelectric ceramic material with ultralow hysteresis electrostrictive strain and preparation method thereof

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